Compounds containing an isophthalate group useful in photography



United States Patent Oflfice 2,721,798 Patented Oct. 25, 1955 COMPOUNDS CONTAINING AN ISOPHTHALATE GROUP USEFUL IN PHOTOGRAPHY Anthony Loria and Edward T. Pesch, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application September- 2, 1953, Serial N0. 378,158

I 11 Claims. (Cl. 956.)

This invention relates tonew compounds containing an isophthalate group and a method for preparing such compounds.

The new "compounds of our invention can be represented by the following general formula:

I. COORl OORi wherein R2 represents an alkyl group, such as methyl, ethyl, n-propyl, etc., or an aromatic radical, such as phenyl, chlorinated phenyl, brominated phenyl, naphthyl, etc. a phenolic radical, such as hydroxyphenyl, hydroxynaphnew compounds containing an isophthalate group. Another object is to provide a method for making such compounds. Still another object is to provide new intermediates which are useful in preparing couplers useful in color photography. Another object is to provide a method for making such intermediates. Another object is to provide photographic emulsions containing the new compounds of our invention. Other objects will become apparent from a consideration of the following description and examples.

The compounds represented by Formula II above are particularly useful in preparing solutions for incorporation in photographic emulsions inasmuch as the ester groups of the isophthalate radical are easily hydrolyzed in alkaline solution (e. g. aqueous sodium hydroxide, aqueous potassium hydroxide, etc.) to produce the alkali metal salts which are quite soluble in the solutions to be added to the photographic emulsion. Also, in the event it is desired to incorporate the new compounds of our invention in photographic developing solutions, the compounds of Formula II are easily incorporated in such developing solutions by simply adding the compound to an thyl and substituted derivatives thereof; or the radical of 7 an open chain ketomethylene compound. The portion of the molecule represented by the above general formula wherein Z is defined is well known in the art of color photography. The portion of the molecule represented by Z is that portion of the compound of Formula I which condenses with the oxidation products formed during development. Such principles are well understood by those skilled in the art of photography and our invention is to be interpreted in the light of thisparticular prior art. However, we have found the compounds represented by the following general formula, which compounds are embraced by Formula I above, are particularly useful for the purposes of our invention:

II. Zr C O 0 CH3 (I) R l -NHb-drr-o- (I) 41 0 O CH:

wherein R has the values given above and Z1 represents a carbanilyl radical having substituted thereon a pyrazolone radical as defined above under Z, a phenolic radical, or a radical containing an open chain ketomethylene group.

Accordingly, it is an object of our invention to provide aqueous alkaline solution as described above. Acidification of these alkaline solutions produces the free carboxylic acids, i. e. compounds of Formula I wherein R1 is a hydrogen atom.

The compounds of Formula II can advantageously be prepared by condensing a compound having the following formula:

III. 0 O CH:

with a aminic coupling component having the following formula:

whereinZ has the values given above. These condensations are advantageously carried out in the presence of an acid-binding agent, such as alkali metal acetates, pyridine, etc., although the use of such an acid-binding agent is not necessary. The condensations are advantageously carried out in the presence of an inert solvent, such as anhydrous acetic acid, acetonitrile, diethyl ether, etc. Temperatures varying from room temperature to the reflux temperature of the reaction mixture can be employed, although we have found that it is quite convenient to simply heat the reaction mixture on the steam bath for a short period of time.

The aminic coupling components represented by Formula IV above have been previously described in the art of color photography, and as noted above, our invention is to be construed in the light of the prior art. For example, a very large number of such aminic coupling components have been previously described and it is not believed essential to enumerate this large body of material herein, inasmuch as this particular embodiment of the invention has been described in detail in a large number of U. S. patents. Typical aminic coupling components have been described in one or more of the following patents:

4 The following schematic diagram will illustrate more Example 3.3,S-dicarbomethoxyphenoxyacetic acid fully the manner whereby the new compounds repre- 002cm sented by the above general Formulas I and II can be I prepared according to our invention. Na 03,011 BrCHzCOZH H91 C 01H 02H 5 (in steps) OO2CH3 NaOH COzCHs SO3H K01 SO3K I then HCl OCH:CO2H

C0211 CO2H C0211 $OC1 COGHa fig i l f Absolute methyl alcohol, 300 ml., was reacted with 13.8 grams (0.6 mol) of clean sodium in a l-liter, CO H Cool 3-necked flask equipped with a water-cooled condenser 2 carrying a drying tube and a mechanical stirrer. The 002GB; CO2CH3 third neck was used for the addition of the other reagents. CHEONa PO15 To the sodium methoxide formed was added first 63 H CH:C0zNa grams (0.3 mol) of 3,5-dicarbomethoxyphenol followed BYCHQCOZN z g by 41.7 grams (0.3 mol) of bromoacetic acid dissolved 010113 (3010113 acid in 100 ml. of absolute methanol with mechanical stirring. SO01 The reaction mixture was heated at reflux on a steam bath with stirring for 18 hours. The precipitate first formed reacted slowly during the heating giving rise to 0CH;COO1 aminic coupler the formation of a much less flocculent new precipitate. After this time the mixture was cooled, poured into 1 liter 00 cm of cold water, and acidified with dilute hydrochloric acid. (3020113 The solid formed was filtered by suction, washed free of acid, and air-dried. 9 The dry material was crystallized from boiling dry coupler xylene. The product was a white crystalline solid and had 002C113 a M. P. of l64-165 c. The following examples will serve to illustrate more Amixed SamP1e of Starting material and PfOduCtShOV/ed fully the manner whereby we practice our invention. a depression of Example 1. 3,5 dichlomformylphenol Example 4.a.-[3,5-dicarb0methoxyphenyflbutyric acid 00211 C001 001cm 02m I NaOCHz -OH soon -0H gg- 1 00211 0001 40 002011 0020113 In a 1-liter, 3-necked standard-taper flask was mixed 156 grams (.855 mol) of 3,5-dicarboxyphenol and 800 ml. of distilled thionyl chloride. (The 3,5-dicarboxyphenol was prepared as given by Heine in B13, 497.) 0020113 The flask was equipped with a mechanical stirrer and a In 500-cc. three-necked flask fitted with a sealed stirrer water-cooled condenser. The mixture was heated at reand a condenser equipped with a calcium chloride drying flux with stirring until complete solution had taken place tube was placed 100 cc. of absolute methanol and 4.6 (about 36 hours). The excess thionyl chloride was disgrams (.2 mole) of clean sodium. Then 21 grams (0.1 tilled otf, first under normal pressure and finally under mole) of 3,5-dicarbomethoxy phenol and a solution of reduced pressure on the steam bath. The product was 16.7 grams (.1 mole) of a-bromobutyric acid in 200 cc. used in the next step without purification. Yield 187 dry xylene were added in sequence to the sodium methgrams, 100 percent of theory. oxide solution. The condenser was inverted and the excess methanol distilled. The mixture from which a solid Example 2-3y5dlcarbomethOxyphenol separated was refluxed 12 hours, cooled, then poured into 0001 CO2CH3 500 cc. of water. The xylene layer was separated and I discarded. The aqueous layer, after being extracted with 0H CH3OH -OH ether, was acidified with dilute (6N) HCl. The clear I oil which first separated solidified on chilling in an ice C0 01 0020113 0 bath. The solid was filtered, recrystallized twice from The crude acid chloride (187 grams, 0.855 mole) 50% HzO-methanol yielding 16.7 grams of white mawhile still warm (to keep it liquid), was added to a thin tenal 149452 (56%) stream to 1 liter of absolute methyl alcohol. The methyl Example yp alcohol had been previously cooled to about 10 C. and wid was stirred vigorously during the addition of the acid 000C113 chloride. The reaction mixture became hot, and a brisk evolution of hydrochloric acid gas took place. The re- OCHZCOOH S0012 action mixture was then cooled to 10 C. and the precipitate formed was filtered by suction and dried in a 000GB:

hot Oven 10 COOCH;

The product was crystallized from 2 liters of dry xylene, thus getting a material melting at 163-5 C. in OCH1GOC1 long white needles. Yield, 138 grams, which is 77 percent of the 179.5 grams theoretical quantity based on the COOCH acid used in making the acid chloride. A suspension of 26.8 g. (0.1 mole) of a-(3,5-dicarbo- Example 6.1 hydroxy N {/3 {2 [2,4 di tert amylpherioxy] 5 [on (3,5-dicarbmeth0xyphen0xy)- The naphthamide used in the above example Was.pre pared as follows:

Thirty g. (0.5 mole) of ethylenediamine and 26.4 g. (0.1 mole) phenyl-l-hydroxy-Z-naphthoate were mixed while cooling in an ice bath. Without cooling the temperature rises above 100 C. With cooling the temperature was kept at 45-50 and after the vigorous reaction subsided, the excess ethylenediamine was removed under acetamido benzamid0}ethyl} 2 naph thamide fiJH IITHz 02 C Ha HOAc CONHCzHtNHCO o1oooH1o- NaOAc 020113 -CHu (l) C O 2 CH3 CtsHn (i) (|)H NH C O C H: O

CONHC2H4NHCO (502011:

0- 'CsHu (i) A mixture of 5.8 g. (.01 mole) of l-hydroxy-N-{fi- [2 (2,4 di tert amylphenoxy) 5 aminobenzami do]ethyl} 2 naphthamide and 2.86 g. (.01 mole) of a-(3,S-dicarbomethoxyphenoxy)acetyl chloride were mixed in 150 ml. of anhydrous acetic acid in a 500-ml. flask and heated on a steam bath for about minutes with occasional shaking. One gram of anhydrous sodium Example r.-1 phenyl 3 {3 {2 {2.4 iii-1m amylphenoxy] 5 [a 3,5 dicarbomethoxyphenoxyy acetamido]benzarnido}benzamido} 5 pyrazolone N=Q-NHCO- BITE: $020113 I com-N HOAc -NHGO- orooonlocoon, HOAc N=CNHCO IFHCOCH20- CaHs-N I 002GB: COCH:

acetate was then added and the heating continued for 1.5 hours, the reaction mixture being protected from moisture with a drying tube during the whole operation. Addition of water to the mixture caused the formation'of a solid which was filtered, washed well with cold water,

The method employed for this reparation was the same as that given in Example 6 above, except that the use of potassium acetate as the condensing agent was found to give better results than sodium acetate. The dry crude solid obtained by adding cold water to the re- ,and dried. The dry solid was crystallized twice from action mixture was crystallized, once from acetonitrile, methyl alcohol, thus obtainingawhite crystalline material and twice from a 50-50 mixture of acetonitrile and melting between 149-451 C., and giving the follown-propyl alcohol. The product obtained had a M. P. of ing analytical results: 149- 150 C. and gave the following analytical figures:

Found Calculated for C 1H5 NsOv Found Calculated for OnHmNso Percent Percent I Percent Percent 0 69. s 70. 0 0 68. 6 as. 3 6.5 5.4 6.0 5.9 5.1 1 5.2 8.0 7.7

. cresol (C. A. vol. 35, pg. 3249) with 2-(2,4'-di-t-arnyl- The pyrazolone componenl emgloyed m the E phenoxy) -5-nitrobenzoyl chloride, followed by reduction ample was prepared as descnbed m the copendmg apph' of the nitro group as described in U. S. Patent 2,589,004.

Example 9.6-{4[2,4-di-tert-amylphenoxy1-3-[u-(3,5-dicarbomethoxyphenoxy) acetamido] benzamido} 2,4- dichl0r0-3-methylphenol C OzCHa o1- NHC oo G H1r(t) Acetommle C10 0 01120- OH: NH: sHnG) C OzCHI (|)H o1 NH0 0- -0 om1(z CH; 511110) C 02011:

1 NHO 0 cmoC cation Serial No. 260,099, filed December 5, 1951, in the The method employed for this preparation was the same names of I. Salminen and A. Weissberger. as that given in Example 8 above. The dry crude prod- Example 8.6{2-[2,4-di-tert-amylphen0xy]-5-[a-(3,5-dicarbomethoxyphenoxy) butyramido] benzamido} 2,4- dichloro-3-methylphen0l OH NH: C OzCH;

Acetonitrile Cl NHC O ClO 0 HO CHz- C 020B;

C OzCH: CaHs (i)H NH0 0 HO Cl NHO O C 02011:

O CsHuU) 01 A mixture of 2.52 g. (.005 mole) of 6-[5-amino-2-(2,4- not was crystallized from n-butyl alcohol. The pure comdi-tert amlphenoxy)benzamido] 2,4 dichloro 3- pound had a M. P. of 208210 C. and analyzed as methylphenol and 1.57 g. (.005 mole) of a-(3,5-dicarbogiven below: methoxyphenoxy)butyryl chloride in 50 ml. of dry acetonitrile was refluxed for 30 min. and let stand for one hr. The reaction mixture was poured into 300 ml. of cold water and stirred mechanically until the oil that had separated solidified. The solid was filtered, washed well with Found Calculated [or OnHuOhNO, cold water and dried. The dry material was crystallized twice. from acetonitrile, using carbon black once. The percent Fem, product had a M. P. of 194-6 C. and gave the follow- 635 mg analysis: 5 3 2 3.7 3.5

Found Calculated for CQHmClZNZOB Percent Percent 0 64.1 64.5

21% 2' The aromatic amine component employed in the above example was prepared by condensing 4-arnino-2,6-dichloro-m-cresol with 4-(2,4-di-t-amylphenoxy)-3-nitroben- The phenol component employed in the above example zoyl chloride, followed by reduction of the nitro group was prepared by condensing 4-amino-2,6-dichloro-mas described in U. S. Patent 2,589,004.

. c solcm Q cmcocl Hm-cocinoo1m I I a l@ c.m

.Acetonitrile C s u was reacted with o-chloronitrobenzene to give 'o-(2;4-di- S-amylphenoxy)nitrobenzene (B. P. 183-6 C./1 mm.).

This latter compound was then reduced With Raney nickel to produce the corresponding amino compound '(M. P.

198-200 C.). This amino compound was then condensed with ethyl p-nitrobenzoylacetate to give 2-(2,4-

' di-S-amylphenoxy)-a-(4-nitrobenzoyl)acetanilide (M. P.

l59l61 C.). This nitro compound was then reduced to the desired amino compound (M. P. 157-8 C.) with Raney nickel.

Example J1:-1-(2,4,6-trichl0r0phenyl) -3-{3- [a'(3,5-dicarbomethoxyphenbxy) n butyramidolbenzamidofy- 5-pyraz0l0ne N=CNHCO 001cm "0:11. 01- N ,7 HOAc NH: cicocno 61 00-011, NaOAc V colon:

. c1 e N='C-NHCO 002cm I NHCOCHO- C0-CH2 COzCHa The product melted at 287-9 C. and gave the following analytical results:

The amine component employed in the above example was prepared as follows: Sodium 2,4 di-5-amylphenate This coupler was prepared by the method employed in Example 6 above. The crude product was crystallized from acetonitrile from which it came out in colorless plates having a melting point of 1879 C.

The aromatic amine component used in the above example has been previously described in U. S. Patent Example 1 2.6-{a-{4 [a- 2,5 -dicarbomethoxyphenoxy n butyramido]phen0xy}acetamid0} 2,4 dichloro- 3-methylphenol COECHa A solution of 4.1 g. (.012 mole) of 6-[a-(4arninophenoxy)acetamido]-2,4-dichloro-3-methylphenol in 25 ml. of dry dioxane was mixed with 3.75 g. (.012) of a-dicarbomethoxyphenoxy)-n-butyryl chloride and the mixture heated on the steam bath for 5 min. Dimethylaniline (1.4 g.) was then added to the mixture and heating continued for 1.5 hrs. longer. The reaction mixture was diluted with an equal volume of water and cooled to 10 C. for 2 hrs. The precipitate formed was filtered, washed, and crystallized twice from ethyl alcohol. There was obtained a slightly pink solid melting at 185-7 C.

In a manner similar to that illustrated in the above examples, the following compounds were prepared:

stood in the art of photography. Instead of incorporating these compounds directly in the emulsion, they can be added to an aqueous alkaline solution to induce hydrolysis and the resulting alkali metal salts of these compounds incorporated in the developing solution. Alternatively, these compounds of Formulas I or II can be incorporated in an organic solvent and added to the photographic emulsion or photographic developing solution and hydrolysis produced in situ.

When employed in the preparation of multilayer color materials, the compounds of Formula II above are particularly useful inasmuch as they do not diffuse in many instances, or diffuse to such a slight degree as to produce C OICHI IYIHCOCHaO on @o omronrmnQ-mzo o 0,011,

OQ-Cfln (t) NHCO HO CsHr-N C 0-CH:

COaGHs (JO-CH2 In like manner, other compounds embraced by Formulas I and II can be prepared according to the description given in Examples I to XII above.

The compounds of Formula II and those of Formula I wherein R1 represents a methyl group can advantageously be incorporated in photographic emulsions by dispersing the compound in an aqueous alkaline medium as mentioned above, whereupon spontaneous hydrolysis of the ester groups occurs to produce the soluble alkali metalsalts. Upon development, these alkali metal salts couple with the oxidation products of the developer to produce the desired color image. These principles are well under- II. COsCH:

$1115 on ITIHCO ono -o onnonamnooQ 01cm oQ-Cdh (c) CrHn (t) m. colon,

CsHr

(iJOaCHl no difficulty. This propertyis particularly useful and is,

' in fact, quite essential to a practical process involving the materials which are suitable for controlling the red, green and blue light of the visible portion of the spectrum. Such controlled colors would, of course, be cyan, magenta and yellow, respectively.

1-3 What we claim as our invention and desire secured by Letters Patent of the United States is:

1. A photographic silver halide emulsion containing a compound selected from those having the following general formula:

wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group, R1 represents a member selected from the group consisting of a hydrogen atom, a methyl group, and an alkali metal atom, and Z represents a mononuclear aromatic radical having substituted thereon a pyrazolone radical containing a radical represented by the following general formula:

wherein R2 represents a member selected from the group consisting of an alkyl group and an aromatic group.

2. A photographic silver halide emulsion containing a compound selected from those represented by the followwherein R represents a member selected from the group consisting of a hydrogen atom, a methyl group, and an ethyl group, and Z1 represents an aromatic radical substituted by a radical containing a pyrazolone radical selected from those represented by the following general formula: I

/N=C- Rz-N wherein R2 represents a member selected from the group consisting of an alkyl group and an aromatic group; a phenolic radical and a radical containing an open chain ketomethylene group.

3. A photographic silver halide emulsion containing a compound selected from those represented by the following general formula:

Z1 C O 0 CH3 0 If, I -NH oH-o- C 0 0 CH3 H Gert.)

051111 (term) wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group, and Z1 represents an aromatic radical containing a radical represented by the following general formula:

wherein R2 represents a member selected from the group consisting of an alkyl group and an aromatic group.

4. A photographic silver halide emulsion containing a compound selected from those represented by the following general formula: V

COOOHa C Hu (tort) wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group and Z1 represents an aromatic radical containing a phenolic radical.

5. A photographic silver halide emulsion containing a compound selected from those represented by the following general formula:

wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group and Z1 represents an aromatic radical containing an open chain ketomethylene radical.

6. A photographic silver halide emulsion containing the compound having the following formula:

OH NHCO CHzO CONHCzENHCO (502GB:

7. A photographic silver halide emulsion containing the compound having the following formula:

CsHr-N C Hz 8. A photographic silver halide emulsion containing the bHn (t) NBC 0 01120- O 2CHa 10. A photographic silver halide emulsion containing the compound having the following formula:

@oomoomrQoocmoorm OzCHa compound having the following formula:

NHCO

C sHn 9. A photographic silver halide emulsion containing the compound having the following formula:

NHCO

NHCOCHMQ O2CH:

11. A photographic silver halide emulsion containing a compound selected from those represented by the following general formula:

OORl

References Cited in the file of this patent UNITED STATES PATENTS 2,540,401 Merckx Feb. 6, 1951 2,569,906 Starke Oct. 2, 1951 2,570,038 Smith et al. Oct. 2, 1951 2,617,820 Gamrath et al Nov. 11, 1952 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTANING A COMPOUND SELECTED FROM THOSE HAVING THE FOLLOWING GENERAL FORMULA 